the formaldehyde challenge (16).pdf · january 2016 old carcinogen category 2 b h 351 new...
TRANSCRIPT
The formaldehyde challenge
Developments on next generation latex binders
32. Hofer Vliesstofftage, 08. – 09.11.2017
Dr. Sören Butz, Synthomer GmbH HOFER VLIESSTOFFTAGE
Introduction to Synthomer
Introduction to the formaldehyde challenge
Route to new FA free cross-linking systems
Formaldehyde generation and analytics
Content
Summary
Synthomer - Top 5 global supplier of emulsion polymers Technical solution provider & broadest chemistry offering & strengthened positon in the US
Divisions & Markets
3
Annual sales volume of Synthetic Latex : 1.56 Mio MT
Broadest Latex offering -> XSBR, XNBR, SA, PA, VA, VACo, VP, ABS, CR, NR*
*: pre-vulcanized
EMEA
Division
ASIA
Division SPECIALITIES
Division
Construction & Coatings
Adhesives & Sealants
Textile & Fibre Bonding
Carpet & Foam
Paper
Health & Protection
Compounds
William Blythe (inorganic specialities)
Performance
Polymers
AMERICAS
Division
Powder Coatings
Monomers
Western
Europe
51 %
USD 1.32 bn
Group revenue
2700
Employees
> 100
Counties
26
Production sites
4
Let us face the Formaldehyde (FA) Challenge – the general view Key raw material with significant Health and Safety implications
Health and Safety Implications for the Textile industry
• multiple regulations on end articles and product labels
• workplace: standards on MAC levels, emission levels,
air quality control requirements…
• limitation of FA emissions to lowest possible level by
process - & technical measures
• regular check on substitution potential
What can be done by the Latex supplier…
• no use of FA in raw material formulations
• ban of FA emitting biocides
• development and implementation of new
options for product cross-linking (-> resin substitution)
Some FA key facts
• naturally occurring compound
• colorless gas with pungent odor
• density: 0,815 g/ cm3
• vapor pressure: 0,43 – 044 MPa
• high water solubility
• estimated production 8,7 Mio t per year (1)
• precursor for industrial resins
(urea, melamine, phenol etc.)
• exemplary resin applications: plywood, coatings,
textiles (as finishing component)
• classification: Toxic (T), corrosive (C)
carcinogen cat 1B, H 350
FA
1) Wiley-VCH, Ullmann´s Encyclopedia of Industrial Chemistry
Let us face the FA Challenge – the regulations view Reclassification to carcinogen category 1 B as strong driver of regulation change
Reclassification in
January 2016
Old
carcinogen category 2 B
H 351
New
carcinogen category 1 B
H 350
Effects on current limits
MAC values *
0,3 ml / m³ (0,3 ppm)
0,6 ml / m³ (0,6 ppm)
TRGS 900*
0,3 ml / m³ (0,3 ppm)
MAC values
• No new limits set yet
• WHO recommendation 0,08 ml/m3
Emmission
values
• No new limits set yet – current TA Luft: 20 mg /m³
• LAI recommendation 5 mg / m³ or 12,5 g/h (Feb 2020)
carcinogen category 1
mutagen category 2
regulated by carcinogen
EU Directive in EU
workplaces
exposure should be as low
as technically possible
using hierarchy of
preventions
*: Germany, individual regulation per country
Cross-linking – high performance by polymer networks Key for may high performance Latices – chemical bonding & finishes
Concept of cross-linking
Creation of chemical bonds leading to an increase of
the molecular weight and the formation of polymer networks
A) Cross-linking during the polymer synthesis
-> monomers with 2 or more double bonds
-> process conditions
B) Cross-linking during the polymer film drying
-> by functional group within the polymer backbone
-> more sophisticated than A
Allows ideal wetting and bonding to the fiber substrate
Cross-linking leads to high performance on:
• elasticity and resilience
• heat resistance
• tensile - / bonding strength
• resistance against solvents, acids, chemicals
• combination of soft handle & none blocking features
• better abrasion resistance
• improved wrinkle behavior
Cross-linking Impact on elasticity and resilience by
Cross-linking technology with N-methylolacrylamide
• special heat reactive co-monomers are included in the polymer chain during polymerization
• reaction at 130°C in the dry state after film formation
Cross-linking during film formation as preferred approach State of the art technology… but FA emissions in ppm range
exhaust air
FA emissions
FA Analytics (1) - A method overview for finished Textiles The method matters – focus on free and hydrolysable FA
Analysis of Textile samples
• analysis of water extract
• photometric identification via colored
reaction products
• detection of free and hydrolyzable FA
• significant differences on
• -> sample size
• -> extraction conditions (temp., time, mixing)
• -> hydrolysis level
• hydrolysis level depending on temp. and pH
• single detection of free FA requires high pH and low
temperature (1)
Some textile test standards
USA: AATCC Test
Japan: MITI – JIS Law 1041, Law 112
UK: Shirley I (“free”) , Shirley II (“released”)
D: DIN ISO 14184-1 (1) Method of de Jong and de Jonge
Photometric FA identification
A) Acetylacetone reaction NASH reaction
B) Chromotropic acid in H2SO4 solution
yellow-green
412nm.
red, 550 nm
FA Analytics (2) - A method overview for finished Textiles A detailed look into the most common tests used for Textiles
Other standards
• Chinese Standard T -18585-2008 most demanding due to steam distillation -> 2,5 g sample (textile or Latex),
steam distillation to 250 ml volume, Acetylaceton
• Total FA content VDL RL03 (paint industry) steam distillation at low pH -> 10 g sample (sample or Latex) ,
50 ml water, 20 ml 20%ige H2SO4, Acetylaceton
hydrolysis level will
increase with extraction
time and temperature
Shirley I < MITI < Law 112
LAW 112 ~ DIN ISO < AATCC
AATCC ~ Shirley II
Method
ho MITI
Law 1041
Japan
Law 112
AATCC
112-82
Shirley I
“free”
Shirley II
“released”
DIN ISO
14184-1
Extraction
conditions
1g
100 ml water
1h, 25 °C
wetting agent
1g
100 ml water
1h, 40°C
1g
50 ml water
20 h, 49°C
sample cage
2g
20 ml water
20min,
25°C
2g
20 ml water
20 h, 49°C
1 g (2,5g)
100 ml water
1 h, 40°C
FA detection
Phloroglucin
photometric
Acetylaceton
photometric
Phloroglucin
photometric
Chromotropic
acid
photometric
Chromotropic
acid
photometric
Acetylaceton
photometric
FA Analytics (3) - FA release at processing TEGEWA method as reference point for FA emissions / FA exhaust emissions by VDI 3862
TEGEWA Method
FA emissions at processing of aqueous based systems
• 1g liquid sample evenly dispersed over 3 g of sand
• heating for 5 min at 160 °C
• emissions are carried over to 2 water filters with 50 and 25 ml water using a nitrogen flow of 200ml/min
• IR heating to prevent condensation in the tube connections
• FA analytics via Acetylaceton method in the collected water made up to 250 ml volume
VDI 3862 (part 6)
Determination of FA in exhaust gases
• 2 water filters (collectors) with 30 ml each
• exhaust gas flow rate 1 L / min (pump system) for 30 min
• typically 30 min measurement time
• heated sampling probe and dust filter (prevent condensation)
• FA analytic via Acetylaceton method
• recording of sample volume, time, temperature,
• cross sensitivities at higher levels of NH3 and with S02
TEGEWA test set up
Aquaizol Bitumen
Bitumen Topside, sanded
Backside (sanded)
Case Study: PES roofing Felts Cross-linking as key for flexible & strong & high temperature resistant PES roofing felts
Application
• PES for bituminous roofing felts
Manufacturing process
• staple fiber or spun bond non woven
• foulard impregnation, foam or liquor
• addition of up to 20 % formaldehyde resins as formulation additive
-> 2 K system with limited pot life (main FA source)
Product requirements
• water resistance - > max reduction of tensile strength of 5%
• high tensile strength -> min. 700 N all 3 key dimensions
• high stiff handle but no kink or crack at flex test
• broad compatibility with thermo-set resins
• high aging stability and filler compatibility
• thermo- dimension stability at 200°C
Current state of the art product offering
• self cross-linking XSBR Latex (FA emissions in ppm range)
• Tg: 35°C, PS: 130 nm, TS: 50%, Viscosity: < 500 mPAs
Targets
• 1 K system, no use of thermo- set resin
-> reduced complexity
-> no pot life limitations
• Cross-linking without FA emissions
PES roofing felt
12
Case study: PES roofing felts Thermo- dimension stability as most demanding product feature, DIN 18192
Targets
• dimensional elongation MD max 1,5 %
• dimensional shrink CD max 1,5 %
• test series: 4 kg load
additional tests (not part of DIN)
• 8 kg load (target max 3 % elongation / 3% shrink)
• force needed for 5 %, 10% and 15 % elongation
• hot tensile strength (180 °C)
Load 4 kg
shrinkage
elongation
elongation
3 samples, 100 mm x 360 mm
10 min 200°C, 5 min conditioning at RT
13
Thermo-dimension stability @ 200°C, 8 kg load • PES non woven, 160 g/sqm,
• 20% coating weight d/d
• product A: market reference, FA releasing
• resins: MF resins, FA releasing
• Innovation: NEW FA free cross-linking XSBR
0
1
2
3
4
5
6
product A product A / 7 ptsresin 1
product A / 7 ptsresin 2
Innovation
elongation (%) shrink (%)
Case study: PES roofing felts – FA free-cross-linking is feasible (1) Strong performance on thermo-dimension stability
Results
• high performance on 200°C
thermo- dimension stability
fulfilled by Innovation product
• no extra MF resin needed
• 1 K solution feasible
14
• PES non woven, 160 g/sqm,
• 20% coating weight d/d
• product A: market reference, FA releasing
• resins: MF resins, FA releasing
• Innovation: NEW FA free cross-linking XSBR
Case study: PES roofing felts – FA free cross-linking is feasible (2) New FA free crosslinking innovation with strong performance on tensile strength
0
100
200
300
400
500
600
700
800
F max (N/ 5 cm) F (N/5 cm), 15 %elongation
F (N/5 cm), 10 %elongation
F (N/5 cm), 5 %elongation
product A / 7 pts resin 1 product A / 7 pts resin 2 Innovation
Tensile strength, RT, MD, DIN 18192
Results
• high performance on tensile
strength fulfilled by Innovation
product
• no extra MF resin needed
• 1 K solution feasible
Summary & Outlook – Synthomer´s green Technology Ultra low FA measurements results – Below detection limits of Law 112 and VDI 3862
FA Analytics
Market reference - self cross-linking
• Latex sample, Free FA ( similar to Shirley I) : 100 – 200 ppm
• Latex sample, TEGEWA: several hundred ppm
Innovation products – FA free self cross-linking
• Latex samples
free FA similar to Shirley I: < 10 ppm, at detection limit
total FA according to VDL R03: < 10 ppm, at detection limit
• FA exhaust emissions
VDI 3862 (part 6) < 0,16 ppm - below detection limit
• Textile samples
according to Japanese Law 112 – below detection limit (5 ppm)
New FA free self cross -lining XSBR Latex
• high performance features based on
FA free cross-linking
• no extra requirements on process
conditions regarding coating / impregnation,
line speed or drying conditions
Summary & Outlook – Synthomer´s green technology How the FA challenge may open new opportunities to the Latex Industry…
New Opportunities by FA free cross-linking
Case Study: PES roofing felts
• 1 K product solution looks now feasible
-> reduction of complexity
-> no handling of extra thermo-set resins
-> no process limitation by pot life
• Lower cross linking temperatures possible
-> energy saving ?
-> higher line output ?
New FA free self cross lining XSBR Latex Our commitment to environmentally
preferred solutions translates into :
FA free cross- linking, APEO free, low VOC,
material efficiency, renewable resources
Several other projects for FA free cross-linking
• PA -> sun blinds, block out curtains
• SA -> PRIPs, Deco Laminates
• XSBR -> alkali resistant glass mesh (EIFS)
• …
The formaldehyde challenge …
Thank you for your attention ! Questions ?
32. Hofer Vliesstofftage, 08.11 – 09.11.2017
Dr. Sören Butz, Synthomer GmbH
HOFER VLIESSTOFFTAGE